Trialkylsilylphenoxysilanes



Patented Sept. 23, 1952- TRI ALKYLSILYLP HENOXYSILAN ES John L! Speier, Jr., Pittsburgh, Pa., assignor to Dow' Gorning Corporation, Midland, Mich., a

corporation of Michigan No Drawing. Application September 18', 1950,

Serial No. 185,514. In Great Britain November 29, 1949 Thisinvention'rel'ates to. trialkylsilylphenoxysilanes vand to theirsmethod of preparation;

Compounds disclosed. herein are novel .com-

positions of matter which are of utility as intermediates in the. preparation of silyl submerely mixing the phenol and silane. Reaction stituted' phenols and other-valuable silicon combegins at once whereupon condensation takes pounds. a .5 place between the phenolic hydroxyl and the This invention relates to -compounds of the silane Y group to produce phenoxysilanes and type either HCl or an alcohol.

I R Silanes of the type RsSiY are well known, commercial materials.. Belong In addition to being valuable intermediates for ell the preparation of other organosiliconcomwhere R is an alkyl radical such as methyl, ethyl p the t k s l p enoxy products of this or octadecyl, R is' alkyl such as methyl, butyl, l5 invention are useful s s -me i a octadecyl and cyclohexylIor-ph'enyl, bhas avalue as thermo expansion fluids- J from 1 t 2 c has value from g t 1 d' The following examples are illustrative only. a value from 1 to 2. 7 EXAMPLE The above compounds may be prepared by v a Y reacting a halophenoxytrialkylsilane, a trialkyl- 0 grams oflfiodlum was ac d 1 9 9 9. of silane and an alkali metal in accordance with the tolueneand 3? lu dl Ut following equation: metal melted. Sufficient tr nethylchloros lane s U r was added to reduce the boilingflpoint of" the 1, liquid mixture to 101 C. 40lgi of p-chlorolnssion. Rl'slY 2,.M- phenoxytrimethylsilane was mixed with 237 g. I a a of 'trimethylchlorosilane and the mixture was I v no f added slowly to the molten sodium at a rate sui- Y a m ficient to keep the reaction mixture boiling v. 'Gg gently. The mixture was agitated and refluxed v (5133) for 'hour after addition of the reactants was th above reaction vR, may be theSamQ-Qr complete. The mixture was thencooled, filtered difierent alkyl radicals,,X'is'halogen Y'is'haloand the filtrate was distilledlwhereuppnz P- gen amoxy and M is an alkali metal, preieb trimethylsilylphenoxy-trimethylsilane was obably Sodium or potassium tained in a yield of 84 percent of theory.

The above reaction is preferably carried out EXAMPLE 2 in an inert solvent which bolls above the meltingpoint of the alkali metal employed Such of EXamp1e 1 a repeatedsolvents include toluene, xylene, benzeneand P potassmm Instead of f' d m 'f n f higher alkyl' ethers and aliphatic hydrocarbons instead of toluene. pz-trlmethylsllylphenoxyboiling above 650 C. 40 trlmethylsllane was obtained. v:.

11111 general, aimiztlrg of the silane and lflalg- EXAMPLE 3 p enoxyslanet s a e odasuspenslon o e V molten alkali metal in the solvent at such a rate To Sodmm and of that the solution is maintained at reflux. Under mane, sumclent meethylcllomsflane such conditions condensation takes place readily all to reducec'the 9 .-9?i i i to produce the compounds of this invention and mlxture 101 A g ze an alkali metal halide or alkoxide. After rep'cm"?phenoxytnmithylsnane and 92 action is complete the desired products are puriethyldlmethylchmmsflalle was added to the fled by distillation sodium at a rate suificlent that the solvent re- The halophenoxysflanes are prepared by 50 fluxed. After addition was complete the mixacting halophenols of th type ture was refluxed for /2 hour. Upon filtering and I distilling the filtrate a mixture of the following R products was obtained: 50g. of p-trimethylsilyl- (HOMQ phenoxytrimethylsilane, 50 g. of p-ethyldi X methylsilylphenoxytrimethylsilane and 55 g. of

i clai s, t (01. zen-448.8) v

with silanes of the type RsSiY in accordance with the method disclosed in. the applicants copiendr ing application filed concurrently herewith'r.

In general, the, reaction is carried out by p ethyldimethylsilylphenoxy ethyldimethylsilane.

EXAMPLE 4 When a mixture of 288.5 grams of olosuonm (CHzhSiO and 120 grams of trimethylchlorosilane is reacted with 50 g. of molten sodium by the procedure of Example 1, the product:

(CHz)aSi[2,-i-[(CH3)as10]2CflH3] is obtained. The properties of this compound are shown in Example 7.

EXAMPLE 6 When a mixture of 235 g. of

(CHa)sSiOCl and 239 g. of trimethylchlorosilane is reacted with 100 g. of sodium by the procedure of E1;- ample 1, the product:

is obtained. The properties of this compound are shown in Example 7.

EXAMPLE '7 By employing the procedure set forth in Examples 1 to 3 inclusive, the compounds shown in the table below were prepared. Inthe table Me designates a methyl radical and Et designates an ethyl radical. V 1

' B. P. mm o 4 Structure Q Press an D L[e3Si(p-OCsH4Sm1m) 132 25 1. 4794 1.900 LIQsSKO-OCnHaSlBIGaL'.Q 128 25 1.4330 0. 910 MeaSi 2,4(MeaSihCnHaO-1 162 24 1. 4843 c299 MeaSi'3l\ie,4(Me5Si)CtH O].. 148 24 1.4892 0.916 Measi 2,4(MeaSi0hCoHa-1 169 19 1.4772 0.927 Mama-04H,4-Me=s1o6H4o- 195 21 1. 5329 0. 974 EtMe=Si(o-MeaSiC4H40) 144 23 1. 4873' 0.9135 EtMe;Si(p-l\le4EtSiC4H4O) 164 25 1. 4841 0. 90s i\le;Si(p-Me:EtSiCtH4O) 144 2:; 1.21306 0. 902 Blessi(2-c6H5-6-1\I3slC5H3O )0.; 20o 24 a) l Isomorphic. 1 M. P. 62.9 C. and 71.6 0.

That which is claimed is: 1. Compounds of the formula in which R represents an alkyl radical, R is a radical selected from the group consisting of '4 alkyl and phenyl radicals, b is an integer of from 1 to 2 inclusive, c is an integer of from 0 to l inclusive, and n is an integer of from 1 to 2 inelusive.

2. Compounds in accord with claim 1 in which R. represents a methyl radical.

8. The method which comprises reacting a halophenoxysilane of the formula asioh (SiRIl)n 9. The method in accord with claim 8 wherein R, represents a methyl radical.

,10. The method which comprises reacting a halophenoxysilane of the formula in which R represents an alkyl radical, R is a radical selected from the group consisting of alkyl and phenyl radicals, X is a halogen atom, c is an integer of from 0 to 1 inclusive, and n is an integer of from 1 to 2 inclusive, with a trialkylsilane of the formula R SlY in which R, is an alkyl radical and Y is a substituent selected from the group consisting of halogen atoms and alkoxy radicals, by contacting the two in liquid phase with a molten alkali metal, whereby there is formed a compound of the formula No references cited. I 

1. COMPOUNDS OF THE FORMULA 